Preparation and characterization of rubidium-beta-alumina by the gel-to-crystallite conversion method

Preparation of Rb-beta -alumina was realized by the gel-to-crystallite conversion method. Reaction of hydrated aluminum hydroxide gel with RbOH in ethanol medium gave rise to the Rb+-inserted pseudoboehmite precursor under wet chemical conditions. The thermal decomposition of the precursor yielded Rb-beta -alumina. The Rb2O:Al2O3 ratio of monophasic Rb-beta -alumina ranged from 1:10 to 1:22. The extended stability in the compositional range is due to the fact that the conduction planes containing Rb+ and O2- ions can have lower occupancy of Rb+ ions for larger sized alkali ions, permitting the steric separation of the adjoining spinel blocks. High-resolution electron microscopy revealed that the decreasing occupancy of alkali ions in the conduction plane is balanced by changing widths of spinel blocks arising from the shift of tetrahedral Al3+ ions to octahedral sites and an accompanying increase in stacking defects. (C) 2000 Elsevier Science Ltd. All rights reserved.

Development of a structured program for conversion to prenex normal form

The method of structured programming or program development using a top-down, stepwise refinement technique provides a systematic approach for the development of programs of considerable complexity. The aim of this paper is to present the philosophy of structured programming through a case study of a nonnumeric programming task. The problem of converting a well-formed formula in first-order logic into prenex normal form is considered. The program has been coded in the programming language PASCAL and implemented on a DEC-10 system. The program has about 500 lines of code and comprises 11 procedures.

A delta13C record of late Quaternary climate change from tropical peats in southern India

STABLE-ISOTOPE ratios of carbon in soils or lake sediments1-3 and of oxygen and hydrogen in peats4,5 have been found to reflect past moisture variations and hence to provide valuable palaeoclimate records. Previous applications of the technique to peat have been restricted to temperate regions, largely because tropical climate variations are less pronounced, making them harder to resolve. Here we present a deltaC-13 record spanning the past 20 kyr from peats in the Nilgiri hills, southern India. Because the site is at high altitude (>2,000 m above sea level), it is possible to resolve a clear climate signal. We observe the key climate shifts that are already known to have occurred during the last glacial maximum (18 kyr ago) and the subsequent deglaciation. In addition, we observe an arid phase from 6 to 3.5 kyr ago, and a short, wet phase about 600 years ago. The latter appears to correspond to the Mediaeval Warm Period, which previously was believed to be confined to Europe and North America6,7. Our results therefore suggest that this event may have extended over the entire Northern Hemisphere.

Characterization of biaxial crystals for tangentially phase-matched frequency conversion

Ultraviolet radiation has been generated by tangentially phase-matched sum-frequency mixing in biaxial L-arginine phosphate (LAP) crystal for the first time using Nd:YAG output at 1064 nm and Rh 6G dye laser output at 560 nm as the two input sources. Characterization has also been made of such a cheap, biaxial crystal for its possible use in devices for tangentially phase-matched short wavelength generation. If the crystal is of proper cut, thickness and quality so that its maximum capability can be exploited it can replace the potassium dihydrogen phosphate (KDP) group of crystals for various applications.

Dynamic coupling between the LID and NMP domain motions in the catalytic conversion of ATP and AMP to ADP by adenylate kinase

The catalytic conversion of adenosine triphosphate (ATP) and adenosine monophosphate (AMP) to adenosine diphosphate (ADP) by adenylate kinase (ADK) involves large amplitude, ligand induced domain motions, involving the opening and the closing of ATP binding domain (LID) and AMP binding domain (NMP) domains, during the repeated catalytic cycle. We discover and analyze an interesting dynamical coupling between the motion of the two domains during the opening, using large scale atomistic molecular dynamics trajectory analysis, covariance analysis, and multidimensional free energy calculations with explicit water. Initially, the LID domain must open by a certain amount before the NMP domain can begin to open. Dynamical correlation map shows interesting cross-peak between LID and NMP domain which suggests the presence of correlated motion between them. This is also reflected in our calculated two-dimensional free energy surface contour diagram which has an interesting elliptic shape, revealing a strong correlation between the opening of the LID domain and that of the NMP domain. Our free energy surface of the LID domain motion is rugged due to interaction with water and the signature of ruggedness is evident in the observed root mean square deviation variation and its fluctuation time correlation functions. We develop a correlated dynamical disorder-type theoretical model to explain the observed dynamic coupling between the motion of the two domains in ADK. Our model correctly reproduces several features of the cross-correlation observed in simulations. (C) 2011 American Institute of Physics. doi:10.1063/1.3516588]

Direct conversion of 13-beta-alkylgonatetraenes into 13-beta-alkylgon-4-en-3-ones

Birch reduction of 8,9-didehydroestradiol-17 beta 3-methyl ether 1 or 9(11)-didehydroestradiol-17 beta 3-methyl ether 2 followed by acid hydrolysis results in a mixture of 19-nortestosterone 8 and 19-nor-9 beta, 10 alpha-testosterone 9 in varying amounts. However, reduction of their acetates with sodium or lithium, tert-butyl alcohol in liquid ammonia and in the presence of aniline affords exclusively 19-nortestosterone. Similarly, 18a-homo-19-nortestosterone 12 is prepared from the acetate of 18a-homoestradiol-17 beta 3-methyl ether, 10.

Molecular assemblies for solar energy conversion - Biomimetic approach

Excitation energy migration followed by electron transfer forms the main components of natural photosynthesis. An understanding of these aspects is essential to reenact the primary processes in laboratory under conditions that are precisely repeatable. Here we describe the state of understanding of the natural process and several model systems designed to harvest solar energy and conversion to useful form of chemical energy. The molecular assemblies constituting the model systems offer a great advantage in terms of better comprehension of the mechanistic aspects and yield valuable information on the design of molecular photonic devices.

Role of neutral metabolites in microbial conversion of 3beta-acetoxy-19-hydroxycholest-5-ene into estrone

Biotransformation of 3 beta-acetoxy-19-hydroxycholest-5-ene (19-HCA, 6 g) by Moraxella sp. was studied. Estrone (712 mg) was the major metabolite formed. Minor metabolites identified were 5 alpha-androst-1-en-19-ol-3,17-dione (33 mg), androst-4-en-19-ol-3,17-dione (58 mg), androst-4-en-9 alpha,19-diol-3,17-dione (12 mg), and androstan-19-ol-3,17-dione (1 mg). Acidic metabolites were not formed. Time course experiments on the fermentation of 19-HCA indicated that androst-4-en-19-ol-3,17-dione was the major metabolite formed during the early stages of incubation. However with continuing fermentation its level dropped, with a concomitant increase in estrone. Fermentation of 19-HCA in the presence of specific inhibitors or performing the fermentation for a shorter period (48 h) did not result in the formation of acidic metabolites. Resting-cell experiments carried out with 19-HCA (200 mg) in the presence of alpha,alpha'-bipyridyl led to the isolation of three additional metabolites, viz., cholestan-19-ol-3-one (2 mg), cholest-4-en-19-ol-3-one (10 mg), and cholest-5-en-3 beta,19-diol (12 mg). Similar results were also obtained when n-propanol was used instead of alpha,alpha'-bipyridyl. Resting cells grown on 19-HCA readily converted both 5 alpha-androst-1-en-19-ol-3,17-dione and androst-4-en-19-ol-3,17-dione into estrone. Partially purified 1,2-dehydrogenase from steroid-induced Moraxella cells transformed androst-4-en-19-ol-3,17-dione into estrone and formaldehyde in the presence of phenazine methosulfate, an artificial electron acceptor. These results suggest that the degradation of the hydrocarbon side chain of 19-HCA does not proceed via C-22 phenolic acid intermediates and complete removal of the C-17 side chain takes place prior to the aromatization of the A ring in estrone. The mode of degradation of the sterol side chain appears to be through the fission of the C-17-C-20 bond. On the basis of these observations, a new pathway for the formation of estrone from 19-HCA in Moraxella sp. has been proposed.

Wet chemical syntheses of ultrafine multicomponent ceramic powders through gel to crystallite conversion

Coarse (BOn/2)-O-n+/xH(2)O (10conversion involving the instability of the metal hydroxide gel brought about by the disruption of the ionic pressure in the gel as a result of the faster diffusion of A(2+) ions through the solvent cavities within the gel frame work. This is accompanied by the splitting of the bridging groups like B-(OH)-B or B-O-B, leading to the breakdown of the gel into crystallites. G-C conversion has advantages as a method of synthesis of ceramics in terms of operational cost and procedural simplicity.

Methanol-to-gasoline (MTG) conversion over ZSM-5. A temperature programmed surface reaction study

The conversion of methanol to gasoline over zeolite ZSM-5 has been studied by temperature programmed surface reaction (TPSR). The technique is able to monitor the two steps in the process: the dehydration of methanol to dimethyl ether and the subsequent conversion of dimethyl ether to hydrocarbons. The activation barriers associated with each step were evaluated from the TPSR profiles and are 25.7 and 46.5 kcal/mol respectively. The methanol desorption profile shows considerable change with the amount of methanol molecules adsorbed per Bronsted site of the zeolite. The energy associated with the desorption process, (CH3OHH+-ZSM5 --> (CH3OHH+-ZSM5 + CH3OH, shows a spectrum of values depending on n.